Process for vulcanizing rubbers in presence of thiophosphoryl disulfides



United States Patent 3,419,521 PROCESS FOR VULCANIZING RUBBERS IN PRES- ENCE 0F THIOPHOSPHORYL DISULFIDES Gerald Scott and Derek Williams, Manchester, England, assignors to Imperial Chemical Industries Limited, London, England, a corporation of Great Britain N0 Drawing. Continuation of application Ser. No. 406,907, Oct. 27, 1964. This application Sept. 15, 1967, Ser. No. 668,258 Claims priority, application Great Britain, Feb. 23, 1960, 6,314/60 13 Claims. (Cl. 260-415) ABSTRACT OF THE DISCLOSURE Bis(dialkylthiophosphoryl)disulphides and the corresponding dicycloalkyl, diaryl and diaralkyl compounds are used in conjunction with conventional sulphur-com taining accelerators and sulphur for the vulcanisation of natural and sulphur-curable rubbers. An increase in activity of the conventional accelerator is obtained, leading to improved properties of the vulcanisate and shorter times of cure, as well as a reduced tendency to premature vulcanisation.

This application is a continuation of application Ser. No. 406,907, now abandoned, which in turn is a continuation-in-part of application Ser. No. 883626, now abandoned.

This invention relates to an improved process for the vulcanisation of rubber and more particularly to the use of certain bis(thiophosphoryl)disulphides in conjunction with conventional vulcanisation accelerators in the sulphur curing of natural and synthetic rubbers.

It has been found that by the addition of certain bis(thiophosphoryl)disulphides not only is the activity of conventional accelerators increased, thus producing vulcanised rubbers having high physical properties in shorter times, but also the tendency of these accelerators to cause premature vulcanisation or scorching is reduced.

Thus according to our invention there is provided a process for the vulcanisation of natural or synthetic rubbers derived to a major extent from diolefin monomers by heating with sulphur and an accelerator characterised in that as accelerator there is used a mixture of a conventional sulphur-containing rubber yulcanisation accelerator and a bis(thiophosphoryl)disulphide of the formula wherein each R is an alkyl, cycloalkyl, aryl or aralkyl group.

As conventional sulphur containing rubber vulcanisation accelerators which may be used in the process of the invention there may be mentioned tetraalkyl thiuram disulphides such as tetramethylthiuram disulphide, tetraethylthiuram disulphide, tetrabutylthiuram disulphide and bispentamethylenethiuram disulphide, tetraalkylthiuram monosulphides such as tetramethylthiuram monosulphide, mercaptobenzthiazole and its metal salts such as zinc mercaptobenzthiazole, mercaptobenthiazyl disulphide, sulphenamides such as cyclohexylbenzthiazyl sulphenamide, tert.-octylbenzthiazyl sulphenamide, tert.-butylbenzthiazyl sulphenamide, N-oxydiethylenebenzthiazyl sulphenamide, diisopropylbenzthiazylsulphenamide, di thiopiperidine, dithiomorpholine, and condensates of sulphenamides such as benzthiazylsulphenamide with alde- Patented Dec. 31, 1968 hydes, and derivatives of dithiocarbamic acid such as zinc 'diethyldithiocarbamate, zinc pentamethylenedithiocarbamate, and dialkyl(dialkylthiocarbamyl)dithiophosphates obtained by reaction of dialkylthiocarbamyl chlorides and dialkyldithiophosphoric acid, for example diisopropyl(diethylthiocarbamyl)dithiophosphate.

The groups each represented by R in the bis(thiophosphoryl)disulphide may be the same or different and as examples of such groups there may be mentioned methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-buty1, sec.-octyl, cyclohexyl and phenyl. It is preferred however to use those compounds in which each R represents an alkyl group which contains at least three carbon atoms, and particularly a secondary or tertiary alkyl group, or cycloalkyl group as these compounds have the greatest eflfect in reducing the tendency of the rubber mix to scorch. These compounds may be prepared for example by interaction of salts of the appropriate dithiophosphates with chlorine, hypochlorous acid or hydrogen peroxide.

The synthetic rubbers which may be vulcanised by the process of our invention are those in which the major part of the components are diolefines, for example polymers of butadiene, isoprene and 2-chlorobutadiene and copolymers of these with minor amounts of acrylonitrile, styrene, methyl methacrylate and other well known polymerisable compounds which may be used in the manufacture of synthetic rubbers.

The vulcanisation of the rubber by heating with sulphur and the accelerator mixtures may be carried out at the temperatures commonly in use and preferably between and C. although higher or lower temperatures may be used if desirable.

The sulphur usage may be that conventionally em ployed, that is amounts between 0.2 and 3.5% of the weight of the rubber. Owing to their activating effect the addition of bis(thiophosphoryl)disulphides permits a reduction in sulphur usage to below 2% of the weight of rubber without loss of curing speed and alfording increased safety fromscorch.

'If desired the natural or synthetic rubber may also contain known adjuvants for the manufacture of rubber compositions for example, fillers, channel and furnace blacks, antioxidants, antiozonants, other accelerator activators, retarders, waxes, blowing agents and pigments. The bis(thiophosphoryl)disulphides are of particular value when used with high abrasion furnace blacks, which are well known to increase considerably the tendency of the conventional rubber mix to scorch, since the reduction in scorch is most pronounced in these circumstances.

(The conventional accelerators and bis(thiophosphoryl) disulphides may be added to the rubber before vulcanisation either separately or in the form of a mixture. The constituents of the mixture together may be used in amount up to 10% of the weight of the rubber and are preferably used in amount between 0.5 and 2%. The proportion of bis(thiophosphoryl)disulphide may be from 15 to 90% of the weight of the mixture and is preferably between 30 and 70%.

As a further feature of our invention we provide new vulcanisable compositions of natural and synthetic rubbers derived to a major extent from diolefin components characterised in that there is contained therein sulphur, a conventional vulcanisation accelerator and a bis(thiophosphoryl)disulphide as hereinbefore defined.

By the use of these bis(thiophosphoryl)disulphides the activity of the conventional accelerator is increased to such an extent that considerable improvements both in rate of cure and physical properties can be obtained. Furthermore, the mixes do not scorch so readily thus permitting longer milling, compounding or other handling times without danger of premature vulcanisation. A further advantage of the use of bis(thiophosphoryl)disul- 3 phides is that rubber vulcanisates prepared employing these compounds have enhanced resistance to attack by ozone.

4 EXAMPLE 4 The following rubber mixes are prepared by compounding on a rubber mill:

Mix H Mix I Mix J Mix K Butadiene-styrene copolymer 100 100 100 100 Stearic acid l l 1. 5 1. 5 1. 5 1. 5 Zinc oxide 3. 5 3. 5 3. 5 3. 5 High abrasion furnace black. 50 5O 50 50 Softener 1 4 4 4 4 Processing oil- 4 4 4 4 Sulphur 1. 8 1. 8 1. 8 1. 8 N-cyclohexylbenzthlazyl sulphenamide 1. 2 1. 2 1. 2 1. 2 Bis(diisopropylthiophosphoryl)disulphide 1. O 0. 5 0. 25 Zinc dinonyldithioearbamate 0.5 0.25

Our invention is illustrated but not limited by the following examples in which all parts are by weight unless otherwise stated.

EXAMPLE 1 The following rubber mixes are prepared by com- Samples of these are cured at 153 C. for diiferent lengths of time and these possess the following properties:

pounding on a mill Time H I J K Tensile Strength (kg./sq.e1n.) 10 116 153 150 10 20 194 209 219 201 A B i8 215 208 20a 204 185 Smoked sheet 100 100 100 Elongation at Break (kg./sq.em.) 10 557 647 580 Stear1eac1d 3 3 3 20 523 409 382 416 Zinc oxide 3-5 3 5 30 500 386 342 419 Hlgh abrasion furnace black 50 50 50 40 45 345 405 g 5 g 5 g 5 5 Modulus at 300% Elongation 10 50 56 64 Newer-55515552155251551555155554.. 5.5 0 5 5.5 38 132 8 it? Bis(diisopropylthiophosphoryl)disulphide 0 1 0.5 40 4 171 155 Mooney Scorch mins.at 140 C.(n1in.+10) 22 22.5 19 21 Samples of these are cured at 141 C. for different lengths of time and these possess the following properties: 30

(Time) A B c EXAMPLES mllPS. il st g (kgilsqxzmi) H 10 19 2 2 273 I The followlng rul?ber mlxes are P p y compound- 277 244 274 lng on a rubber mill: 277 190 241 Elongation at Break, percent 10 547 540 576 20 552 386 468 M 1 1 t3007 El (k 30 33 $6 3 5 o uusa ongation g.sq.ern. 10 l 1 1 a g0 14% 209 188 MlXL MIX M 0 1s 214 Mooney Scorch nlins. at 120 o. (Min.+10) 24 29. 75 27.5 g ggi z g g Zinc oxide IIIIIIIIIIIIII 3.5 3.5 EXAMPLE 2 Hlgh abrasion furnace black. 50 50 gogtelrller 4 4 r up ur 2.5 2.5 Rupber imxes D and E Slmllar to mugs and C re N-tert.-oetyldinethylthiocarbamylsu1phenamide 0.5 0.25 SpfiCtlVBlY in Example are prepared using 111 Place O bis(dilsopropylthiophosphoryl)disulphide 0.25 the N-cyclohexylbenzthlazyl sulphenamlde 0.25 part of tetramethyl thiuram disulphide. Samples of these are cured at 141 C. for difierent lengths of time and these Samples of these are cured at 141 C for different have the followin ro rties:

g p p6 lengths of time and give the followmg propertles:

Time D E (mins.)

Tensile Strength (kg./sq.em.) g8 31% Time L M 4 30 249 214 Tensile Strength (kg.lsq.cm.) 10 267 249 Elongation at Break, percent 1(1)) 20g 252 20 263 260 2 5 0 30 252 249 30 443 342 Elongation at Break 10 515 544 Modulus at 300% Elongation (k ./s .om.)...-

129 20 452 501 5 30 472 490 I 30 183 210 Modulus at 300% elongation 10 160 130 Mooney Scorch mms. at 120 C. (mm.+10) 10. 75 19. 75 20 175 162 30 162 153 Mooney Scorch mlus. at 120 C. (min.+10) 17.25 26 EXAMPLE 3 Rubber mixes F and G similar to mixes A and B respectively in Example 1 are prepared using in place of the N-cyclohexylbenzthiazyl sulphenarnide 0.5 part of EXAMPLE 6 tert.-octylbenzthiazyl sulphenamide. The following rubber mixes are prepared by compound- Samples of these are cured at 141 C. for different ing on a rubber mill: lengths of time and these have the following properties:

Natural rubber smoked sheet Tlme F G Stearic acid 3 Te s e t t a/ q- 5 i id 35 30 255 239 Elongation at Break, percent 10 446 555 70 High abrasion furnace black 50 38 29 3% Softener 4 2 Modulus 51300 2,, Elongation (kg./sq.cm.) 11 1 65 101 Sulphur 2.5

2 122 191 30 167 217 Tert.-octylbenzthlazylsulphenam1de 0.5 M00118}! $001011 1111115. at C (1 n-+l0) 27- 7 1- 7 5 Samples of these are cured at 141 for diflierent lengths O timum time of cure minutes 30 20 20 of tlme and the properties of the vulcanisates and the 2 3 1 strengtg g Mod us at 300 5 b1s(th1ophosphoryl)disulphides used are detailed below. Extension at brgak 480 515 445 Mooney scorch at 140 (minutes 25. 5 18. 5 24 Time of Cure Bis(diisopropyl- Bis (di-syclohexyl- Bis(di-see.-butyl- Bis(di-sec.-octyl- (minutes) thiophosphoryD- thiophosphoryD- thiophosphoryl)- thiophosphoryD- disulphide disulphide disulphide disulphide Tensile Strength kgJcmJ 10 68 42 170 87 262 273 266 276 233 254 245 260 Modulus 300% 10 47 32 85 58 20 175 171 182 151 30 188 189 191 170 Elongation at Break, percent 10 414 396 518 414 20 475 501 465 551. 30 403 436 410 490 Mooney Scorch at 120 (minutes 10) 42. 5 38 40. 5

EXAMPLE 9 EXAMPLE 7 The following rubber mixes are prepared by compound- Samples of these are cured at 153 C. for different lengths of time the properties of the vulcanisates and the bis(thiophosphoryl)disulphides used being detailed below. Results using no bis(thiophosphoryl)disulphide are included for comparison.

The following rubber mixes are prepared by compounding on a rubber mill:

R S T U V W Natural rubber smoked sheet- 100 100 100 100 100 100 Stearic acid 3 3 3 3 3 3 Zinc oxide 3. 5 3. 5 3. 5 3. 5 3. 5 3. 5 High abrasion furnace black 50 50 50 50 50 50 Softener 4 4 4 4 4 4 Tert.-octylbenzthiazylsulphenamide 0. 5 0. 5 0. 5 0. 5 0. 5 0. 5 Sulphur 2. 5 1. 5 1. 0 1. 5 1. 5 1. 0 Bis (diisopropy phosphoryl) disulphide 0. 5 1. 0 1. 0

The Mooney Scorch time, optimum time of cure at 141 of these mixes and shear modulus of the vulcanisates so obtained are as follows:

Optimum cure time (minutes) 32 35 4O 27 22 27 Relative shear modulus 33 27 25 29 31 31 Mooney Scorch at 120 (minutes-H0)" 25. 5 34. 5 40.3 36. 8 40. 8 43 Time of Cure N 0 bis (thiophos- Bis (diisopropyl- Bis (dicyelohexyl- Bis(di-sec.-butyl- (minutes) phoryD-disulphide thiophosph0ryl)- thiophosphoryD- thiophosphoryD- disulphide disulphide disulphide Tensile Strength, kg./em. 10 129 191 56 154 20 236 198 217 197 30 221 189 228 211 Modulus 300% 10 47 38 29 72 20 124 162 139 154 30 142 175 156 166 Elongation at Break, percent 10 794 692 580 587 20 563 392 472 403 30 472 353 451 399 Mooney Scorch at 140 (minutes 10) 15 18. 5 19 20 We claim:

0 1. In a process for the manufacture of vulcanised nat- EXAMPLE 8 ural rubber and sulphur-curable synthetic rubbers derived The following rubber mixes are prepared by compounding on a rubber mill:

The optimum time of cure at 153 of these mixes and properties of the vulcanisates so obtained are as follows:

to a major extent from diolefin monomers which comprises compounding said rubber with sulphur and a conventional sulphur-containing rubber vulcanisation accelerator selected from the group consisting of tetraalkylthiuram disulphides, tetraalkylthiuram monosulphides, mercaptobenzthiazyl disulphide, sulphenamides and derivatives of dithiocarbamic acid and heating said rubber to vulcanise it; the improvement which comprises having present during said vulcanisation a bislthiophosphoryl) disulphide of the formula wherein each R is a member of the group consisting of alkyl, cycloalkyl and aryl groups.

2. A process as claimed in claim 1 wherein each R is an alkyl group containing at least 3 carbon atoms.

3. A process as claimed in claim 2 wherein each R is a member of the group consisting of secondary and tertiary alkyl groups.

4. A process as claimed in claim 1 wherein the total amount of conventional sulphur-containing rubber vulcanisation accelerator and bis(thiophosphoryl)disulphide is from 0.5 to of the weight of rubber.

5. A process as claimed in claim 4 wherein the total amount of conventional sulphur-containing rubber vulcanisation accelerator and bis(thiophosphoryl)disulphide is from 0.5 to 2% of the weight of rubber.

6. A process as claimed in claim 1 wherein the bis- (thiophosphoryl)disulphide comprises from to 90% of the total of conventional sulphur-containing rubber vulcanisation accelerator and bis(thiophosphoryl)disulphide.

7. A process as claimed in claim 1 wherein the bis(thiophosphoryl)disulphide comprises from to of the total of conventional sulphur-containing rubber vulcan- H isation accelerator and bis(thiophosphoryl)disulphide.

8. A process as claimed in claim 1 wherein the amount of sulphur is between 0.2 and 3.5% of the weight of the rubber.

9. A process as claimed in claim 8 wherein the amount of sulphur is less than 2% of the weight of the rubber.

10. A process as claimed in claim 1 wherein the heating is carried out at a temperature between and C.

11. A process as claimed in claim 1 wherein said rubber is compounded with a furnace black in addition to sulphur, conventiontal sulphur-containing rubber vulcanisation accelerator and bis(thiophosphoryl)disulphide.

12. A vulcanisable composition of a member of the group consisting of natural rubber and sulphur-curable synthetic rubbers derived to a major extent from diolefin monomers characterised in that there is contained therein sulphur, a conventional sulphur-containing rubber vulcanisation accelerator selected from the group consisting of tetraalkylthiuram disulphides, tetraalkylthiuram monosulphides, mercaptobenzthiazyl disulphide, sulphenamides and derivatives of dithiocarbamic acid and a bis(thiophos phoryl)disulphide of the formula wherein each R is a member of the group consisting of alkyl, cycloalkyl and aryl groups.

13. A process for the manufacture of vulcanised natural rubber and sulphur-curable synthetic rubbers derived to a major extent from diolefin monomers as set forth in claim 1 in which said conventional sulphur-containing rubber vulcanisation accelerator is selected from the group consisting of tetramethylthiuram disulphide, tetraethylthiuram disulphide, tetrabutylthiuram disulphide, bispentamethylenethiuram disulphide, tetramethylthiuram monosulphide, mercaptobenzthiazole, zinc mercaptobenzthiazole, cyclohexylbenzthiazyl sulphenamide, tert.-octylbenzthiazyl sulphenamide, tert.-butylbenzthiazyl sulphenamide, N-oxydiethylenebenzthiazyl sulphenamide, diisopropylbenzthiazyl sulphenamide, dithiopiperidine, dithiomorpholine, condensates of benzthiazyl sulphenamide with aldehydes, zinc diethyl-dithiocarbamate, zinc pentamethylenedithiocarbamate and diisopropyl(diethylthiocarbamyl) dithiophosphate.

References Cited UNITED STATES PATENTS 6/1937 Romieux et al 1853 11/1965 Kendall et a1. 260459 

